聚苯撑乙炔螺旋异构体的结构和吸收光谱性质研究
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摘要
利用自主装的方法,以苯乙炔单元分子结构为基础,参考基元分子聚合的可能位置异构特征,设计一系列聚苯撑乙炔的特征三维螺旋分子结构。利用量子化学密度泛函理论计算方法对聚苯撑乙炔低聚物的结构、稳定性、激发能、轨道组成、激发态电子跃迁性质等进行了理论研究。从理论上系统地分析其聚合物链空间几何结构和性质对聚合物光谱性质的影响。本研究可为聚苯撑乙炔分子材料光谱性能的调制和设计提供基本的理论支持。
By using the self-assembling method,based on the phenylene ethynylene molecular structure,a series of three dimensional helical structures of poly-phenylene ethynylene molecules were designed referring to the possible polymerization sites of the primary molecular unit.The oligomer structures,stability,excitation energies,orbital components,excited states electron transition properties of polyphenylene ethynylene were theoretical investigated by quantum chemical method under density functional theory basis.A systematical analyses have been conducted for the influence of spherical configuration and properties onto the spectral properties of the oligomers.This study may provide reliable basic theoretical support to the modification,modulation and improvement purposes of polyphenylene ethynylene polymer optical performance and the design of novel molecular optical materials.
By using the self-assembling method,based on the phenylene ethynylene molecular structure,a series of three dimensional helical structures of poly-phenylene ethynylene molecules were designed referring to the possible polymerization sites of the primary molecular unit.The oligomer structures,stability,excitation energies,orbital components,excited states electron transition properties of polyphenylene ethynylene were theoretical investigated by quantum chemical method under density functional theory basis.A systematical analyses have been conducted for the influence of spherical configuration and properties onto the spectral properties of the oligomers.This study may provide reliable basic theoretical support to the modification,modulation and improvement purposes of polyphenylene ethynylene polymer optical performance and the design of novel molecular optical materials.
引文
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[2] HOEBEN F J M,JONKHEIJM P,MEIJER E W,et al. About supramolecular assemblies of π-conjugated systems.[J].Chem Rev,2005(105):1491.
[3] THOMAS III S W,JOLY G D,SWAGER T M.Chemical sensors based on amplifying fluorescent conjugated polymers.[J].Chem Rev,2007(107):1339.
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[5] CHEN A J,HSU I J,WU W Y,et al.A fluorescent organic nanotube assembled from novel p-phenylene ethynylene-based dicationic amphiphiles.[J].Langmuir,2013(29):2580.
[6] KIM J.Assemblies of conjugated polymers:Intermolecular and intramolecular effects on the photophysical properties of conjugated polymers.[J].Pure Appl Chem ,2002(74):2031.
[7] SCHWARTZ B J.Conjugated polymers as molecular materials:how chain conformation and film morphology influence energy transfer and interchain interactions.[J].Annu Rev Phys Chem,2003(54):141.
[8] YANG J S,YAN J L ,HWANG C Y,et al.Probing the intrachain and interchain effects on the fluorescence behavior of pentiptycene-derived oligo(p-phenylene-ethynylene)s.[J].J Am Chem Soc,2006(128):14109.
[9] KIM J,SWAGER T M.Control of conformational and interpolymer effects in conjugated polymers.[J].Nature,2001(411):1030.
[10] GUNNAR J,SAJID M,SCHULTE M,et al.Flexibility of shape-persistent molecular building blocks composed of p-phenylene and ethynylene units.[J].J Am Chem Soc,2010(132):10107.
[11] KANG Y K,LEE O-S,DERIA P,et al.Helical wrapping of single-walled carbon nanotubes by water soluble poly(p-phenyleneethynylene).[J].Nano Lett,2009(9):1414.
[12] LEVITUS M,SCHMIEDER K,RICKS H,et al.Steps to demarcate the effects of chromophore aggregation and planarization in poly(pheny-leneethynylene)s.1.Rotationally interrupted conjugation in the excited states of 1,4-bis (phenylethynyl)benzene.[J].J Am Chem Soc,2001(123):4259.
[13] KIM J,LEVITSKY I A,MCQUADE D T,et al.Structural control in thin layers of poly(p-phenyleneethynylene)s:Photophysical studies of langmuir and langmuir-blodgett films.[J].J Am Chem Soc,2002(124):7710.
[14] MAGYAR R J,TRETIAK S,GAO Y,et al.A joint theoretical and experimental study of phenylene–acetylene molecular wires.[J].Chem Phys Lett,2005(401):149.
[15] CHEN G W,SONG F L,XIONG X Q,et al.Fluorescent nanosensors based on fluorescence resonance energy transfer (FRET).[J].Ind Eng Chem Res,2013(52):11228.
[16] LIU R Y,SHIOTSUKI M,MASUDA T,et al.Synthesis and chiroptical properties of hydroxyphenylglycine-based poly(m-phenyleneethynylene-p-phenyleneethynylene)s.[J].Macromolecules,2009(42):6115.
[17] VENDRELL M,ZHAI D,CHENG J E,et al.Combinatorial Strategies in Fluorescent Probe Development.[J].Chem Rev,2012(11):4391.
[18] YASHIMA E,MAEDA K,FURUSHO Y.Single- and double-stranded helical polymers:synthesis,structures,and functions.[J].Acc Chem Res,2008(41):1166.
[19] TAN C,PINTO M R,KOSE M E,et al.Solvent-induced self-assembly of a meta-linked conjugated polyelectrolyte.Helix formation,guest intercalation,and amplified quenching.[J].Adv Mater,2004(16):1208.
[20] MCRAE R L,PHILLIPS R L,KIM I-B,et al.Molecular recognition based on low-affinity polyvalent interactions:selective binding of a carboxylated polymer to fibronectin fibrils of live fibroblast cells.[J].J Am Chem Soc,2008(130):7851.
[21] GAN Q,BAO C,KAUFFMANN B,et al.Quadruple and double helices of 8-fluoroquinoline oligoamides.[J].Chem Int Ed,2008(47):1715.
[22] BREDAS J-,BELJONNE D,COROPCEANU V,et al.Charge-transfer and energy-transfer processes in π-conjugated oligomers and polymers:A molecular picture.[J].Chem Rev,2004(104):4971.
[23] FRISCH M J,TRUCKS G W ,SCHLEGEL H B,et al.Gaussian 09,Revision C.01,Gaussian,Inc.,Wallingford CT,2010.
[24] LI N,JIA K,WANG S F ,et al.Theoretical study of spectroscopic properties of dimethoxy-p-phenylene-ethynylene oligomers:Planarization of the conjugation backbone.[J].J Phys Chem A,2007(111):9393.